Method of producing hydroxylated dehydroabietic acid compounds



; Patented Jan.9,1945

.METHOD OFLPRODUCING HYDROXYLATED- DEHYDROABIETIC ACID COMPOUNDS William P. Campbell, Newark', 'Del.; assignor to. T I

Hercules Powder'Company, Wilmington; -Del-.', acorporationnf Delaware 1 No: Drawing. Application-June 27, 1942,"

' serialame 13, Claims." won zen-97in I This invention relates .toan improved "method for, producing, hydroxylated, 'de hydroabietic.v acid. 1

compounds.,,

' Hydroxy derivatives ofidehydroabietic' acid have i been described in j the literature. Howevencno satisfactory, process capable of. providing good yieldslo'f 'such'phydroxyproducts has been known thantheoreticalinterest;a 4 v Now, iii-accordance ,with this invention, ,ithas been V discovered; that improved] yields of ,fhy+

' and the. products'haveltherefore acquired no more droxylated}'dehydrcabietic, ,acid compounds. cone taining the hydrocarbon .nucleus of dehydroe abietic acid'm'ay be obtained by. heating a halogenated; derivative of. neither dehydroabietic .acid,

or .a compound derived from dehydroabietic acid,

and containing the hydrocarbonnucleus of'dedroxide;

Theimprovedprocess maybe-illustrated by the droxydehydroabietic acid produced was recovered in the'same manner as in Example I;

The hydroxylated' derivatives of dehydrbf abietic acid and dehydroabietici acid compounds" containing, the hydrocarbon nucleus of dehydroabietic', acid produced in" accordance with the process "of'this invention will' contain one or more hydroxyl groupsastsubstituents inthe aromatic nucleus. The number of' h'ydroxyl groups introduced willbe dependent on the number'of halogenatoms substituted'inithe aromatic nucleus of the halogenated dehydroabietic acid-compound. used. in thelprocess; The process is particularly adapted .-.to production ';of the mono hydroxy defhydroabietic, acid or, Idehydroabietic acid compoundsfrom theu n'ono halogenated products; The aromatic nucleusof 'the dehydroabietic acid molecule contains ,three' unsubstituted positions.

- However, two of the positions. are more reactive hydroabietic acid compound which forms a starting point-for-the described processmay be proev duced in anydesired-mannerr A convenient pro-.

followingspecific examples. Allj'parts expressedl in,. the examples representtparts. by weight-r'unless otherwise indicated.v I

' Example Thirty parts of monobroinodehydroabietic acid, prepared. by, Nomination .of' mono vsulfodehydroabietic acid, were heated with 215 parts of water and parts of potassium hydroxide in an auto-' clavevin ,a nitrogen. atmosphere atxa temperature oil 300% C; for;'1B.;hours; .flThe reaction mixture resulting was diluted withiwater, filteredwhile. warm and the solutionacidified'with hydrochloric acid,v Thegmono hydroxydehydroabietic acid which precipitated from the solution was. recoveredanddried; Thetyield was 13 parts.

Fifty parts of, monobroniodehydroabietic acid,

be-obtainedinaccordance with the procedure described-in U. s; Patent12;207,890 to Edwin R'.

were heated with"1500 parts of 1'2.% aqueous soe dium chydroxide ,infa-,.copper vesseLinQa'n autoclave ,atga. temperature ofng290l Ch for,15.' hoursin,ai nitrogen atmosphere. The monohydroXy-v dehydroabietid- .acid was; recovered as. in. Ex-

ampleIw ExampleIIL Forty parts ofmono chlorodehydroabietic acid were heated with 1000 parts" of I 12%" aqueous-so I dium hydroxide as inExample II. The mono hythan "the thirdwandlaccordingly the substitution of,hydroxylgroups will usually. be confined to-thel substitution of either one or twohydroxyl groups. p

The halogenated: dehydroabiet-ic acid or decedure involves directhalogenation of 'sulfo de-t rivatives of dehydroabietic acid such as mono sulfo dehydroabietic; acid, sulfonated derivatives.

of?dehydro'abietic acid compounds such as sulfonateddehydroabietyl alcohol, sulfonated dehydroabietinal; sulfonated dehydroabietane, sulfonated salts -of-=dehydroabieticacid, sulfonated ethers of dehydroabietyl alcohoLandsulfonated alkoxide'spf dehydroabietyl alcohol; The direct halogen'ation of the sulfonated derivatives in aque'oussolutionprovides high yields of the halogenated products;

preparation of s the: halogenated derivatives may Littmannt otherme'thods of preparing thehalogenated dehydroabietic acid compoundsmay be. used ifdes'ir'ed." The loro'minatedand chlorinated- .derivatives'will'be particularly :preferred'imthe' 3 process since they are most easily prepared. Also theiiodo and fluoro derivatives are le'ssreactive in thepresent process and thus the yields are' lower and' are not as desirable from-this standpoint. i In carrying out the process of the invention.

Thus, bromination of mono sulfodehydroabietic acid in aqueous solution pro- I vides a 92 yield of the mono bromodehydroabietic acid. The sulfonated dehydroabietic acid or sul it fonated'dehydroabietic acid compounds used in:

either analkali metal hydroxide or an alkaline earth metal hydroxide may be employed. The alkali metal hydroxides are preferred. Thus, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, etc. may be used. The reaction between the alkali and the halogenated dehydroabietic acid or halogenated dehydroabietic acid compound is conveniently carried out in the presence-of water. Thus, an aqueous solution of the alkaline material may be used. The amount of water is not critical and, generally speaking, the alkaline material may be used in aqueous solutions having concentrations from about 1% to about 50% by weight. The amount of alkali used will generally be an excess over that required for complete reaction with the halogenated dehydroabietic acid or dehydroabietic acid compound. v e

In carrying out the process a temperature in the range of about 200 C. to about 320 C. will provide the hydroxylated product in good yields. The reaction is more rapid at the higher temperatures and accordingly a reaction temperature of about 280 C. to about 310 C. will be preferred. The time required for completion of the reaction will depend on the specific alkali used, the temperature of reaction, the specific halogenated material used, as well as on other factors. The time of reaction generally falls within the range of about 3 hours to about 20 hours.

In some instances it may be desirable to em-.

ploy a catalyst for the reaction. The catalysts which may be used will be those which are known to be efiective in replacement of halogen atoms by hydroxyl groups. Metallic copper, cupric salts or cuprous salts such as cuprous bromide, cuprous chloride, cuprous oxide, cupric oxide, etc. are desirable.

After completion of the heating period, the alkaline solution is generally cooled and filtered to remove any undissolved components. It is then acidified with any suitable acid, such as a mineral acid. The hydroxylated derivative, being insoluble or partially insoluble in water, will precipitate and may be recovered by filtration. Other methods for recovering the hydroxylated products which will be obvious to those skilled in the art may be employed if desired.

The hydroxylated dehydroabietic acid or hydroxylated dehydroabietic acid derivatives which are prepared in accordance with the improved process of this invention are useful for a number of purposes, such a for anti-oxidants, for raw materials to provide resinous polymers and other, reaction products.

What I claim and desire to protect by Letters Patent is:

1. The method of producing a hydroxylated dehydroabietic acid compound containing the hydrocarbon nucleus of dehydroabietic acid which comprises heating a compound selected from the,

group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane. esters of dehydroabietic acid, salts of dehydroabietic acid, ethers of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with an alkaline material selected from the group consisting of alkali metal and alkaline earth'metal hydroxides.

2. The method of producing a hydroxylated dehydroabietic acid compound containing the hydrocarbon nucleus of dehydroabietic acid which comprises heating a compound selected from the group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane, esters of dehydroabietic acid, salts of dehydroabietic acid, ethers of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 280 C. to about 310 C. with an alkaline material selected from the group consisting of alkali metal and alkaline earth metal hydroxides.

3. The method of producing a hydroxylated dehydroabietic acid compound containing the hydrocarbon nucleus of dehydroabietic acid which comprises heating a compound selected from the group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane, esters of dehydroabietic acid, salt of dehydroabietic acid, ethers of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with an alkali metal hydroxide.

4. The method of producing a hydroxylated dehydroabietic acid compound containing the hydrocarbon nucleus of dehydroabietic acid which comprises heating a compound selected from the group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane, esters of dehydroabietic acid, salts of dehydroabietic acid, ethers of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with potassium hydroxide.

5. The method of producing a hydroxylated dehydrcabieteic acid compound containing the hydrocarbon nucleus of dehydroabieteic acid which comprises heating a compound selected from the group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane, esters of dehydroabietic acid, salts of dehydroabietic acid, ether of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and. which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with an alkaline earth metal hydroxide.

6. The method of producing a hydroxylated dehydroabietic acid compound containing the hydrocarbon nucleus of dehydroabietic acid which comprises heating a compound selected from the group consisting of dehydroabietic acid, dehydroabietyl alcohol, dehydroabietinal, dehydroabietane, esters of dehydroabietic acid, salts of dehydroabietic acid, ethers of dehydroabietyl alcohol, and alkoxides of dehydroabietyl alcohol and which compound contains a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with an alkaline material selected from the group consisting of alkali metal and alkaline earth metal hydroxides in the presence of a catalyst for the reaction. s

7. The method of producing a hydroxylated dehydroabietic acid which comprises heating de hydroabietic acid having a halogen substituent in its aromatic nucleus at a temperature within the range of about 200 C. to about 320 C. with an alkali metal hydroxide.

8. The method of producing a hydroxylated dehydroabietic acid which comprises heating dehydroabie'tic acid having a halogen 'substituent v in its aromatic nucleus at a temperature within the range of about 280 C. to about 310 C. with an alkali metal hydroxide.

' -9. The method-of producing hydroxylated' dehydroabietic acid which comprises heating dehydroabieteic acid having a halogen substituent in its aromatic nucleus at a temperature within the range of about 280? C. to about 310 C. with an alkali metal hydroxide in the presence of a catalyst for the reaction. v

10. The method of producing a hydroxylate 'dehydroabietic acid which comprises heating dehydroabietic acid having a brominesubstituent in its aromatic nucleus at a temperature within the range of about 280 C. to about 310 C; with an alkali metal hydroxide.

11. The method of producing a hydroxylated dehydroabietic acid which comprises heating dehydroabietic acid having a chlorine substituent in itsaromatic nucleus at a temperature within the range of about 280 C. to about 310C. with an alkali metal hydroxide.

12. The methodjof producing a monohydroxylated dehydroabietic acid which comprises heating dehydroabietic acid having one bromine substituent in its aromatic nucleus at a temperature within the range of about 280 C. to about 310'.

- C. with an alkali metal hydroxide.

13. The method of producing a monohydroxylated dehydroabieteic acid which comprises heating dehydroabieteic acid having one chlorine substituentin its aromatic nucleus at a temperature within the range of about 280 C, to about 310 C. with an alkali metal hydroxide.

WILLIAM P. CAMPBELL. 

